Heterodi- [MAg, MAu (M = Pd, Pt)], tri- [PdAg2, PtAg2, PtAu2, Pt2M (M = Ni, Pt, Cd, Hg)], and tetranuclear (Pt2Ag2, Pt2Au2) 1,1-ethylenedithiolato complexes

The reactions of [M(PPh3)(2){S2C=C{QO)Me}(2)}] [M = Pd (1a), Pt (1b)] with AgClO4 and PPh3 or with [Au(PPh3)(OCMe2)]ClO4 afford heterodinuclear [{M(PP h3)(2)}{M'(PPh3)}(2){S2C=C{C(O)Me}(2)}]-(ClO4)(2) [M = Pd, M' = Ag (2a), M = Pt, M' = Ag (2b), An (4)] or trinuclear [{M(PPh3)(2)}{M'(PPh3)}(2){S2C=C{ C(O)Me}(2)}]-(ClO4)(2) [M = Pd, M' = Ag (3a), M = Pt, M' = Ag (3b), Au (5)] 1,1-ethylenedithiolato complexes, depending on the molar ratio of the reag ents. We have recently reported that, in the absence of added PPh3, the rea ctions of [Pt{S2C=C{C(O)Me}(2)}L-2] [L = PPh3 (1b), L-2 = 1,5-cyclooctadien e (cod) (1c)] with AgClO4 produce the heterotetranuclear derivatives [{PtL2 }(2)Ag-2{S2C=C{C(O)Me}(2)}(2)}](ClO4)(2) [L = PPh3 (6a), L-2 = cod (6b)], w hich have been used now as efficient transmetallating agents toward gold, p latinum, mercury, nickel, copper, or cadmium metal centers to give new type s of 1,1-ethylenedithiolato complexes: [{Pt(PPh3)(2)}(2)Au-2{S2C=C{C(O)Me}( 2)}(2)]-(ClO4)(2) (7), [(PtL2)(2)M{S2C=C{C(O)Me}(2)}(2)](ClO4)(2) [L-2 = co d, M = Pt,(8), L = PPh3, M = Hg (9)], [{Pt(PPh3)(2)}(2){S2C=C{C(Me)=O}(2)}( 2)Ni](ClO4)(2) (10), and [{Pt(PPh3)(2)}(2){S2C=C{C(Me)=O}(2)}(2){M(OClO3)(2 )}] [M = Cu (11), Cd (12)1. The crystal structures of two different solvate s of 7 and that of 11 have been determined. All of these display two [Pt(PP h3)(2)}{S2C={C(O)Me}(2)} moieties but, whereas in 7 they bridge two gold(I) centers through the sulfur atoms, in 11 they chelate the copper(II) center through the oxygen atoms. The last one is the first example of such a coor dination mode for the 2,2-diacetyl-1,1-ethylenedithiolato ligand.